Photographic layer capable of receiving writing



-water resisting substances.

Patented Mar. 9, 1943 PHOTOGRAPHIG LAYER CAPABLE OF RECEIVING wnrrmeGale F. Nadeau and, Henry R. Couch, Rochester, N. Y., assignors toEastman Kodak Company, Rochester, N. Y., a corporation of New JerseyApplication September 25, 1940, Serial No. 358,274

13 Claims.

This invention relates to a sensitized photographic element andparticularly to an element provided with a pigmented layer designed toreceive writing.

It is a well known practice to waterproof paper, cloth and similarmaterials which are highly susceptible to moisture by the application ofnon-moisture absorbing layers to the surfaces of these materials. Asapplied to the various sensitized photographic products, it is thepractice to employ in these layers cellulose esters, polymerized vinylcompounds and similar A photographic paper such as a direct positivepaper, which is designed to render a positive image in a minimum oftime, requires a support which will not be substantially wetted byprocessing solutions and can be delivered in practically a drycondition, often within the space of a few minutes. Such a paper hasbeen described in the prior 1153?. Patent No. 1,933,824, grantedNovember 7, 1

Frequently it is desired to write or print with ink onto the back ofsuch a paper and this is generally prevented by the thoroughness withwhich the paper has been waterproofed. Likewise the surface of the papermay refuse to take pencil markings unless it is especially prepared toreceive pencil records.

The same difflculties are encountered in the use of sensitized tracingcloths such as are described in the prior U. S. Patent 2,117,814 grantedMay 17, 1938. While the tracing cloth may be satisfactorily waterproofedso as to resist the softening effect of processing solutions it isgenerally impossible to imprint satisfactory pencil or ink recordsthereupon. Likewise photographic film which is now in general use willnot readily take pencil or ink impressions; By its very nature the filmis resistant to aqueous solutions such as ink and the smooth surfaceswill not retain pencil marks.

The principal object of the present invention is to overcome thesedimculties by providing sensitive photographic products with a pigmentedlayer which will take either ink or pencil.

This object is accomplished by depositing upon a water proof support alayer consisting of an inorganic pigment such as titanium oxide, baryta,chalk, or lithopone; a hydrophilic material such as gelatin and acellulosic material such as cellulose organic and inorganic esters andcellulose ethers. We may also use resins in place of the cellulosiccompounds, and, in the preferred embodiment of our invention, titaniumoxide as the pigment.

In the accompanying drawing, Fig. 1 is a cross section illustrating therelation of the pigmented layer to the support and emulsion layer.

Fig, 2 is a cross section of a sensitive photographic paper providedwith cellulose nitrate waterproofing layers, the pigmented layer, and anemulsion layer adhesively joined to the support.

Fig. 3 is a cross section illustrating the appplil0 cation of theinvention to a sensitized tracing cloth. The pigmented layer is disposedon one side of the waterproofed cloth support and the emulsion layer isadhesively joined to the other side.

Fig. 4 is a cross section illustrating the general arrangement of layerscomprising a sensitive photographic film provided with a titanium oxidelayer capable of receiving ink and pencil marks.

In the operation of our invention we apply the titanium oxide containinglayer from solvent solutions of which the following is typical.

, Per cent 1 Cellulose nitrate 1.2 Gelatin 1.2 Acetic acid 2.0 Water 5.0Acetone 50.0 Methanol 40.6

To this formula is added the titanium oxide. For our purposes a 25%concentration is sufficient. The pigmented sub is then coated upon awaterproof support and allowed to dry.

We will now describe our invention by particular reference to theaccompanying drawing. In the general operation of the invention as shownin Fig. 1, the support I0 is coated on both sides with the subbinglayers l4 and I5. These layers may consist of the same or differentmaterials.

0 For instance, I4 may be cellulose nitrate, cellulose acetate, orcellulose acetate-propionate but usually l5 consists of cellulosenitrate, ordinary gelatin being applied over this to serve as anadhesive layer I6 for the emulsion l'l. Other- Wise, if I 5 is notcellulose nitrate. adhesive layers consisting of for instance gelatinand a synthetic resin or gelatin coated from a solution of water, aceticacid, acetone, and methanol are used to get the proper adhesion andflexibility.

The titanium oxide containing layer (8 is applied directly over layer I4and may contain in addition to the oxide, gelatin and any celluloseester.

Fig. 2 illustrates the use of a paper support ll coated with thecellulose nitrate on both sides, layers l9, although these may be othercellulose esters or mixed esters; the adhesive layer 20 which may begelatin joins the emulsion layer I! to layer l9. On the opposite sidethe mixed titanium oxide, gelatin, and cellulose nitrate layer 2| iscoated over the nitrate layer 19, The support may be a glossy paperwhich has previously been baryta sized and according to the invention isthen waterproofed, emulsion coated on the glossy side, and pigmentcoated on the back.

Fig. 3 shows the cloth support l2 double coated with cellulose layers 22and 23 which may consist of the same, different, or mixed celluloseesters. The adhesive subbing layer 24 joins the emulsion H to layer 23and on the opposite side of the support the mixed titanium oxide,gelatin, and cellulose ester layer [8 is coated over layer 22. Layers 22and 18 may contain the same or difi'erent cellulose esters.

Fig. 4 illustrates the method of application of the titanium oxidecontaining layer 18 to a cellulose ester support l3 which may be opaqueor transparent. In this case due to the water resitsant nature of thecellulose ester support it is not necessary to coat it withwaterproofing layers; therefore subbing layers 25 and 26 comprising, forinstance, gelatin are applied followed directly by the emulsion layer Hon one side, and on the opposite side, the mixed titanium oxide, gelatinand cellulose ester layer. Should l8 contain a cellulose ester otherthan cellulose nitrate it may be desirable to incorporate into layer 25a material such as a synthetic resin to aid in-obtaining the properflexibility and adhesion between layers l8 and 25.

It will be noted that the general technique of our invention consists inapplying an emulsion layer and a, pigmented layer to a waterproofsupport. Should the pigmented layer comprise a cellulose ester whichdoes not adhere well to the waterproof support it may be desirable toadd to the subbing layers I4, 22, or 25 a material such as a resin.Should the emulsion layer not adhere well or give the proper flexibilitywhen coated upon subbing layers such as 15 or 23 a material such as asynthetic resin is added to the adhesive layer. This technique is morefully described in U. S. Patents 2,096,616; 2,096,617; 2,096,675. In analternative method we use a gelatin subbing solution containing a highpercentage of acetone, for instance, 66% acetone, water, 25% methanol,2% gelatin and 2% acetic acid to sub a cellulose acetate layer which isto receive an emulsion.

The following example further illustrates the manner of carrying out ourinvention.

A glossy double-weight baryta-coated photographic paper was coated onboth sides with a dope ,of cellulose nitrate of the followingcomposition:

Per cent Cellulose nitrate 4 Amyl acetate 76.4 Methanol 9.5 Acetone 9.5Triphenyl phosphate 0.6

This is followed by a thin coating of the following composition on theback side:

I On top of this second coat on the back side of the paper is applied acoating from a dope of the following composition:

Per cent Cellulose nitrate 1.2 Gelatin 1.2 Acetic acid 2.0 Water 5.0Acetone 50.0 Methanol 40.6

to which 3% titanium oxide has been added. On the glossy side of thepaper was coated a gelatin layer from a solution of which the followingis typical.

It is not always necessary to double coat a support with a celluloseester but some supports having substantially long protruding fibers arebest rendered completely waterproof and smooth by such a technique.

The cellulose nitrate which we use as a constituent of the pigmentedlayer or the subbing layers may be a highly alcohol soluble onecontaining 10-12%, preferably 11% of nitrogen. Instead of a single lightsensitive emulsion layer we may employ a plurality of differentiallylight sensitive emulsion layers containing light filter or sensitizingdyes or color formers or other material whichadapt the element to use inthe taking or reproduction of color pictures in color. Here again we arenot limited to any specific cellulose ester for use throughout theelement.

Having thus described our invention, what we declare is new and desireto secure by Letters Patent of the United States is:

1. A sensitive photographic element designed to receive writingcomprising, a support coated on both sides with a subbing layer of amaterial selected from the group consisting of gelatin and celluloseester, a pigmented layer consisting of a mixture of an inorganicpigment, gelatin, and a cellulose compound over the subbing layer on oneside of said support and on the opposite side a light sensitive emulsionlayer adhesively joined to a subbing layer.

2. A sensitive photographic element designed to receive writingcomprising, a support coated on both sides with a cellulose estersubbing layer, a pigmented layer consisting of a mixture of titaniumoxide, gelatin, and a cellulose ester over the subbing layer on one sideof said support, and on the opposite side a light sensitive emulsionlayer adhesively joined to a subbing layer.

3. A sensitive photographic element designed to receive writingcomprising, a support coated on both sides wth a cellulose ester subbinglayer, a pigmented layer consisting of a mixture of titanium oxide,gelatin, and cellulose nitrate over the subbing layer on one side ofsaid support, and on the opposite side a light sensitive emulsion layeradhesively joined to a subbing layer.

4. A sensitive photographic element designed to receive writingcomprising, an opaque support coated on both sides with a cellulosenitrate waterproofing layer, a pigmented layer consisting of a mixtureof titanium oxide, gelatin, and cellulose nitrate over the waterproofinglayer on one side of said support, and on the opposite side a lightsensitive emulsion layer adhesively joined to the waterproofing layer.

5. A sensitive photographic element designed to receive writingcomprising, a paper support coated on both sides with a cellulosenitrate waterproofing layer, a pigmented layer consisting of a mixtureof titanium oxide, gelatin, and cellulose nitrate over the waterproofinglayer on one side of said support, and on the opposite side a lightsensitive emulsion layer adhesively joined to the waterproofing layer.

6. A sensitive photographic element designed to receive writingcomprising, a cloth support coated on both sides with a cellulosenitrate waterproofing layer, a pigmented layer consisting of a mixtureof titanium oxide, gelatin, and cellulose nitrate over the waterproofinglayer on one side of said support, and on the opposite side a lightsensitive emulsion layer adhesively joined to the waterproofing layer.

7. A sensitive photographic element designed to receive writingcomprising, a paper support coat- 8. A sensitive photographic elementdesigned to receive writing comprising, a paper support coated on bothsides with a cellulose acetatepropionate waterproofing layer, apigmented layer consisting of a mixture of titanium oxide, gelatin, andcellulose nitrate over the waterproofing layer on one side of saidsupport, and on the opposite sidea light sensitive emulsion layeradhesively joined to the waterproofing layer.

9. A sensitive photographic element designed to receive writingcomprising, a paper support coated on both sides with a celluloseacetate waterproofing layer, a pigmented layer consisting of a mixtureof titanium oxide, gelatin, and cellulose acetate over the waterproofinglayer on one side of said support, and on the opposite side a lightsensitive emulsion layer adhesively joined to the waterproofing layer.

10. A sensitive photographic element designed to receive writingcomprising, a cloth support coated on both sides with a celluloseacetate waterproofing layer, a pigmented layer consisting of a mixtureof titanium oxide, gelatin, and cellulos nitrate over the waterproofinglayer on one side of said support, and on the opposite side a lightsensitive emulsion layer adhesively joined to the waterproofing layer.

11. A sensitive photographic element designed to receive writingcomprising, a cloth support coated on both sides with a celluloseacetatepropionate waterproofing layer, a pigmented layer consisting of amixture f titanium oxide, gelatin, and cellulose nitrate over thewater-.- proofing layer on one side of said support, and on the oppositeside a light sensitive emulsion layer adhesively joined to thewaterproofing layer.

12. A sensitiv photographic element designed to receive writingcomprising, a cloth support coated on both sides with a celluloseacetate waterproofing layer, a pigmented layer consisting of a mixtureof titanium oxide, gelatin, and cellulose acetate-propionate over thewaterproofing layer on one side of said support, and on the oppositeside a light sensitive emulsion layer adhesively joined to thewaterproofing layer.

13. A sensitive photographic element designed to receive writingcomprising, a cellulose acetate support coated on both sides with acellulose nitrate subbing layer, a pigmented layer consisting of amixture of titanium oxide, gelatin, and cellulose nitrate over thesubbing layer on one side of said support, and on the opposite side alight sensitive emulsion layer.

GALE F. NADEAU. HENRY R. COUCH.

